The luminescence spectra of Eu3+ at a T-h point-group site in the hexanitritolanthanate systems Cs2NaEu((NO2)-N-14)(6), Cs2NaEu((NO2)-N-15)(6), Rb2NaEu((NO2)-N-14)(6), Cs2LiEu((NO2)-N-14)(6), and Cs2NaY((NO2)-N-14)(6):Eu3+ have been recorded between 19500 and 10 500 cm(-1) at temperatures down to 3 K. The spectra comprise magnetic-dipole-allowed zero phonon lines, odd-parity metal-ligand vibrations, internal anion vibrations, and lattice modes, with some weak vibrational progressions based upon vibronic origins. With the aid of density functional theory calculations, the vibrational modes in the vibronic sidebands of transitions have been assigned. The two-center transitions involving NO2- stretching and scissoring modes are most prominent for the D-5(0) -> F-7(2) hypersensitive transition. The onset of NO2- triplet absorption above 20 000 cm(-1) restricts the derived Eu3+ energy-level data set to the F-7(J) (J = 0-6) and D-5(0,1) mulfiplets. A total of 21 levels have been included in crystal-field energy-level calculations of Eu3+ in Cs2NaEu(NO2)(6), using seven adjustable parameters, resulting in a mean deviation of similar to 20 cm(-1). The comparison of our results is made with Eulf in the double nitrate salt. In both cases, the fourth-rank crystal field is comparatively weaker than that in europium hexahaloelpasolites.